Tertiary cycloaliphatic hypohalites



Patented Apr. 13, 1954 UNITED STATES ears FFICE TERTIARY CYCLOALIPHATIOHYPOHALITES No Drawing. Application July 30, 1951, Serial No. 239,403

9 Claims.

This invention relates to a new class of organic hypohalites and to aprocess for effecting a novel rearrangement reaction thereof.

Certain organic hypohalites, particularly the hypochlorites, are known.These known hypochlorites include tertiary hypochlorites in which thetertiary carbon is singly bonded to three organic radicals, usuallyhydrocarbon, with the fourth valence of the tertiary carbon beingsatisfied by the hypochlorite radical. These known tertiaryhypochlorites undergo ready degradation, in some instancesspontaneously, to form an alkyl halide and a ketone as illustrated belowfor tertiary amyl hypochlorite which decomposes to acetone and ethylchloride:

CzHa-JJ-OCI r CHzCOCHa+ 0211501 C lHa As can be seen, this degradationreaction involves the loss of one of the organic radicals bonded to thetertiary carbon from the main structure of the molecule with theformation of a molecule of an organic chloride. This loss is obviouslyundesirable in that it represents a high weight loss and allows theproduction of only lower molecular weight products than the startingmaterials.

It is an object of this invention to provide a new class of tertiaryorganic hypohalites. A further object is to provide a new class oftertiary organic hypohalites which do not undergo cleavage but rearrangeto a product having the same molecular weight as the startinghypohalite. Another object is to provide a novel method of preparingomega-haloketones. Other objects will appear hereinafter.

These and other objects of this invention are accomplished by providinga new class of tertiary hypohalites, the tertiary cycloaliphatichypohalites, and a proces for effecting their rearrangement toomega-haloketones.

In the new class of tertiary hypohalites which have now been discovered,at least two and preferably only two of the valences of each tertiarycarbon atom which is bonded directly to a hypohalite radical aretogether joined through at least one divalent organic radical of from 3to 7 aliphatic chain members, preferably solely carbon, to form at leastone and preferably only one aliphatic ring, any remaining valence ofsaid tertiary carbon atom being satisfied by an organic radical,preferably solely hydrocarbon, which isfree of Zerewitinoff-activehydrogen. These new tertiary hypohalites are cyclic tertiary 2hypohalites in which a tertiary carbon atom, which also carries thehypohalite radical, is an annular member of at least one and preferablyonly one organic ring, said rings containing 4 to 8 aliphatic ringmembers and being prefer ably saturated alicyclic, with the remainingvalence, if any, of said carbon being satisfied by an organic radical,preferably solely hydrocarbon such as alkyl or aryl, which is free ofZerewitinofiactive hydrogen.

These new cyclic tertiary hypohalites can be schematically representedby the following general structural formula: V

and R is a divalent organic radical of 3m 7 aliphatic chain members andcan include hetero atoms such as oxygen, nitrogen, or sulfur as well ascarbon atoms.

These new cyclic tertiary hypohalites are characterized by a new andunexpected behaviour in that they do not decompose under chemicalactivation but undergo a true rearrangement wherein no molecule is splitoff, i. e., the rearranged product is of the same molecular weight asthe starting hypohalite. These new tertiary cycloaliphatic hypohalitesundergo rearrangement to omega-haloketones upon chemical activation asby heating or through the use of catalysts, such as by irradiation withultraviolet light or sunlight. The omega-haloketones have the samemolecular weight as the tertiary cycloaliphatic hypohalites from whichthey are prepared. This rearrangement may be schematically representedby the following general equation:

wherein R. R, and X are as described above. This 3 new rearrangement isclaimed in my copending continuation application Serial No. 347,825,filed April 9, 1953.

The following examples, in which the parts given are by weight. aresubmitted to illustrate further and not to limit this invention.

Example I Chlorine is bubbled into a nearly homogeneous solution of 37.5parts of l-methylcyclopentanol and 30 parts of sodium hydroxide in 700parts of water over a period of two hours with stirring at ice/waterbath temperatures, at such a rate that saturation is effected. Thereaction mixture thus obtained separates into a lower yellow oil phaseand an upper clear aqueous :phase- The lower oil phase is extracted withthree fifty-part Example II A forty part sample of crudel-methylcyclopentyl hypochlorite is heated at 35-40 C. under a pressureof 80 mm. of mercury for ten minutes, during which time the materialchanges in color from yellow to green, with no evidence of exothermicreaction. The crude product so obtained is distilled atroom temperatureunder a pressure of 2 mm. of mercury into a trap cooled in a solid'carbon dioxide/acetone bath. There is thus obtained 35.5 parts (90%yield) of 6-chlorohexan- 2-one' as a colorless liquid boiling at 85'-86C. under a pressure of 16mm. of mercury.

Additional samples of I-methylcyclopentyl hypochlorite are alsorearranged to 6-chlorohexan- 2-one by treatment in. solution in methanolor suspension in water with aqueous solutions of ferrous sulfate.

The preparation of a representative member of the new class of cyclictertiary hypohalites of this invention (l-methylcyclopentylhypochlorite) has been illustrated in Example I by the halogenation' ofthe corresponding cyclic tertiary alcohol inan aqueous alkaline medium,specifically aqueous sodium hydroxide solution; Other such aqueous mediacan also be used including aqueous solutions of the alkali metalhydroxides.

and carbonates and aqueous suspensions of the alkaline earth metalhydroxides and carbonates. Other methods can also be used in thepreparation of these new cyclic tertiary hypohalites; for instance theymay be prepared in non-aqueous media such as ether, chloroform, carbontetrachloride, etc., by reaction of the corresponding alcohol withchlorine monoxide, C120,. or with a solution of anhydrous hypochlorousacid in. thosesolvents.

As has been disclosed previously herein, the new cyclic tertiaryhypohalites of this invention are those wherein each carbon carrying ahypohalite group is a tertiary carbon of whose valences at least two andpreferably only two are together joined through one to two divalentorganic radicals of from 3- to 7 aliphatic chain members, which caninclude hetero atoms such as oxygen, nitrogen, and sulfur to form analiphatic ring or rings, and the remaining valence of the tertiarycarbon, if any, is satisfied by an organic radical free ofZerewitinoif-active hydrogen and of less than seven carbons for eachtertiary hypohalite radical inthe molecule. Because of readieravailability of the necessary intermediates and greater ease inpreparation, the preferred cyclic tertiary hypohalites of this inventionare those wherein the halogen is chlorine and the tertiary carboncarrying the hypochlorite'radical has two of its valences togetherjoined through a. divalent hydrocarbon radical of 3 to 7, and preferably4 to 5, aliphatic chain carbons,pref erably a divalent saturatedaliphatic hydrocarbon radical, to form an aliphatic ring and theremaining valence of the tertiary carbon is' satisfied by a hydrocarbonradical of 1 to 6 carbons which is most preferably also free ofaliphatic unsaturation.

Specific examples of the broad class of cyclic tertiary hypohalitesofthis invention include.

the tertiary cycloaliphatic hypochlorites and hypobromites, for examplel-methylcyclobutyl hypochlorite, 1-ethyl-l-methylcyclopentylhypobromite, l-phenyl-3rethylcyclohexyl hypochlorite,l-propylcycloheptyl hypochlorite, l-phenyl- 3(p-chloropheny-l)-cyclohexyl. hypochlorite,v 1,4- dimethyll-piperidyl hypochlorite, thehypochlorites of 3-ethyl-3hydroxytetrahydrothio phene-l-dioxide and3-methyl-3-hydroxytetrahydrofurane hypochlorite, Q-decahydronaphthylhypochlorite,- 1 ,2-ethylenebis(l-cyclopentyl hypochlorite) These cyclictertiary hypohalites. can be prepared according to the procedure setforth in detail in Example I by substituting the requisite halogen, e.g., bromine, for the chlorine and for the 1.-methylcyclopentanolthereinemployed the corresponding. alcohols such asl-methylcyclobutanol, 1 ethyl 4 methylcyclopentanol, 1phenyl-3ethylcyclohexanol,, l-propylcycloheptanol, l-phenyl-3(p-chlorophenyl) -cyclohexanol, 1,4-dimethyle4-piperidinol,

3-ethyl-3-hydroxytetrahydrothiophene-l-dioxide,3-methyl-3-hydroxytetrahydrofurana, 9-'-hydroxy-decahydronaphthalene,and 1,2-ethylenebis(l-cyclopentanol).

As previously stated, herein, these two cyclic tertiary hypohalitesundergo ready rearrangement with no weight loss to an omega-halogensubstituted ketone-the. halogen, of. course, being. that. of the.hypohalite used. The halogensubstituted ketone products of thisrearrangement will be of the, samemolecular weight asathe startinghypohalite and will contain the halogen,

separatedfromthe ketonetcarbon by the divalent organic radical which.joins the two valences. of the tertiary carbon ofthe, starting cyclictertiary hypohalite, with: the remaining valence of. the

ketone carbon being, satisfied by the same radical which. satisfies. theremaining valence of the tertiary carbon in the startin hypohalite. Inthose instances wherein. all three valences. of the tertiary carbon ofthe starting hypohalite, are

involved in apolycyclic structure, a mixturev of.

products will be obtained; varying with which one of the fused rinstructuresisbrokenin the rearrangement. In. those instances. wherein thestarting cyclic tertiary hypohalite containsmore than one suchtertiaryhypohalite group, the rearranged product will correspondingly containthe. same numberv of halogen-substituted ketone" moieties. Specificexamples of the: omega-halo- 5. en-substituted ketones obtained by thisrearrangement include -bromopentan-2-one from 1- methylcyclobutylhypobromite, phenyl 7-ch1orod-m'ethyl-n-heptyl ketone from 1-phenyl-5-methylcyclooctyl hypochlorite, 2-(4-chlorobutyl) cyclohexanone andG-chlorocyclodecanone from Q-decahydronaphthalene hypochlorite,1,11-dichloro-5,7-undecanedione from methylenebis-lcyclopentylhypochlorite.

This rearrangement can be readily effected by maintainin the startinghypohalites at temperatures in the range 30 to 100 C. for periods oftime ranging from 1 to 250 minutes. Longer periods of time, of course,may be used, but little or no advantage is ained thereby since therearrangement is essentially complete in this temperature range in mostcases in as short a time as 5 to 30 minutes. Higher temperatures can, ofcourse, also be used in the rearrangement, but again little advantage isgained thereby and the tendency for some of the cyclic tertiaryhypohalites to undergo the rearrangement reaction with extreme rapidityin the higher temperature ranges, e. g., of the order of 100 to 150 C.,prompts the use of temperatures in the range 40 to 60 C.

The rearrangement reaction can be carried out in bulk or in solution ina normally liquid unreactive solvent, e. g., the halogenatedhydrocarbons such as chloroform, carbon tetrachloride,

methylene chloride, chlorobenzene; the aromatic hydrocarbons, e. a,benzene, toluene, and the xylenes. The rearrangement can also be carriedout in aqueous systems, i. e., two-phase or heterogeneous systems, sincethe startin cyclic tertiary hypohalites are generally water-insoluble.Thus, if desired, the crude reaction mixture obtained in the normallyused preparative method of the starting tertiary cyclic hypohalite (i.e., the halogenation of the requisite cyclic tertiary alcohol in anaqueous alkaline medium) can be placed directly under conditionsnecessary for the rearrangement and the rearranged product. i. e., theomega-halogen-substituted ketone isolated directly by normal proceduresof distillation or extraction and subsequent distillation, or, in thecase of solids, filtration. However, because of the greater puritynormally obtained in the rearranged product, i. e., theomega-halogensubstituted ketone, it is preferred to isolate the startingcyclic tertiary hypohalite from the reaction mixture and to carry outthe rearrangement either in bulk or in organic solution.

The rearrangement can be carried out at lower temperatures and inshorter times through the use of suitable catalysts, e. g., ultravioletlight or sunlight. Thus, the rearrangement can be carried out at roomtemperature in as short a time as 15 minutes by irradiation of thestarting cyclic tertiary hypohalite with ultraviolet light, in bulk, orin solution.

This rearrangement reaction is quite surprising in that no molecule oforganic halide is split out, nor is any cyclic ketone formed. As hasbeen disclosed in detail previously, rearrangement, not degradation,surprisingly occurs producing only an omega-haloketone.

This new class of cyclic tertiary hypohalites, in addition to theirutility in undergoing this surprisin rearrangement to produce thedesirable omega-halogen-substituted ketones, are also useful asbleaches, as chlorinating agents, as reagents for preparation ofhalohydrins, and generally as sources of active halogen.

The omega halogen-substituted ketones result 'I ing from the surprisingrearrangement of the' new cyclic tertiary hypohalites of this inventionare in themselves useful as otherwise difiicultly obtainableintermediates for organic syntheses and as compounds of biologicalinterest for their pesticidal and fungicidal properties.

As many apparently widely different embodierits of this invention may bemade without:

departing from the spirit and scope thereof, it is to be understood thatthis invention is not limited to the specific'embodiments thereof exceptas defined in the appendedclaims.

I claim:

1. A tertiary cycloaliphatic hypohalite in which a tertiary carbon atomin a cycloaliphatic rin is bonded directly to a hypohalite radicalselected from the class consisting of hypochlorite and hypobromiteradicals.

2. A tertiary cycloaliphatic hypochlorite in which a tertiary carbonatom in a cycloaliphatic ring is bonder directly to a hypochloriteradical.

3. A cyclic tertiary hypohalite in which a tertiary carbon atom isbonded directly to a hypohalite radical selected from the classconsisting of hypochlorite and hypobromite radicals and at least two ofthe valences of said tertiary carbon atom are joined together through atleast one divalent organic radical of from 3 to 7 aliphatic chainmembers to form an aliphatic ring, any remaining valence of saidtertiary carbon atom bein satisfied by an organic radical free ofZerewitinoii-active hydrogen and of from 1 to 6 chain members perhypohalite radical in the molecule.

4. A cyclic tertiary hypohalite in which a tertiary carbon atom isbonded directly to a hypohalite radical selected from the classconsisting of hypochlorite and hypobromite radicals and two to three ofthe valences of said tertiary carbon atom are joined together through,respectively, one to two divalent hydrocarbon radicals of from 3 to 7aliphatic carbon atoms to form an aliphatic ring, any remaining valenceof said tertiary carbon atom being satisfied by a hydrocarbon radicalfree of Zerewitinoff-activ hydroen and of from 1 to 6 carbon atoms.

5. A cyclic tertiary hypochlorite in which a tertiary carbon atom isbonded directly to a hypochlorite radical and two to three of thevalences of said tertiary carbon atom are joined together through,respectively, one to two divalent hydrocarbon radicals of from 3 to 7aliphatic carbon atoms to form an aliphatic ring, any remaining valenceof said tertiary carbon atom being satisfied by a hydrocarbon radicalfree of Zerewitinofi-active hydrogen and of from 1 to 6 carbon atoms.

6. A cyclic tertiary hypochlorite in which a tertiary carbon atom isbonded directly to a hypochlorite radical and two of the valences ofsaid tertiary carbon atom are joined together through a divalent organicradical of from 3 to 7 aliphatic chain members to form an aliphaticring, the remaining valence of said tertiary carbon atom bein satisfiedby an organic radical free of Zere- Witinoff-active hydrogen and of from1 to 6 chain members.

'7. A cyclic tertiary hypochlorite in which a tertiary carbon atom isbonded directly to a hypochlorite radical and two of the valences ofsaid tertiary carbon atom are joined together through a divalenthydrocarbon radical of from 3 to 7 aliphatic carbon atoms to form analiphatic 7. ring, the remaining valence of said tertiary carbon atombeing satisfied by a. hydrocarbon radical free of Zerewitinoif-activehydrogen and of from 1 to 6 carbon atoms.

8. A cyclic tertiary hypochlorite in which a tertiary carbon atom isbonded directly to a hypochlorite radical and two of the valences ofsaid tertiary carbon atom are joined together through a divalentsaturated aliphatic hydrocarbon radical of from 3 to '7 aliphatic carbonatoms to form an aliphatic ring, the remaining valence of said tertiarycarbon atom being satisfied by an alkyl radical of 1 to 6 carbon atoms.

a 9; The. chemical compound l-methyl'cyclopentyl hypochlorite.

References Cited in the file of this patent UNITED STATES PATENTS NumberName Date 1,938,175 Deanesly Dec. 5, 1933 2,132,342 Jackson Oct. 4, 19382,132,345 Reichert et a1. Oct. 4,1938 2,194,703 Kroeger Mar. 26, 19402,370,392 Boon Feb. 27, 1945

1. A TERTIARY CYCLOALIPHATIC HYPOHALITE IN WHICH A TERTIARY CARBON ATOMIN A CYCLOALIPHATIC RING IS BONDED DIRECTLY TO A HYPOHALITE REDICALSELECTED FROM THE CLASS CONSISTING OF HYPOCHLORITE AND HYPOBROMITERADICALS.
 9. THE CHEMICAL COMPOUND 1-METHYLCYCLOPENTYL HYPOCHLORITE.